Telomerization process using sulfonated triarylphosphine and transition metal

ABSTRACT

A process for the telomerization of dienes with a telomerizing compound containing a mobile hydrogen atom is disclosed wherein the reaction between the diene and the telomerizing agent is effected in the presence of a catalytic system comprising a water-soluble sulfonated triaryl phosphine compound, preferably a water-soluble salt of a mono-, di-, or trisulfonated triphenyl phosphine and a transition metal compound, preferably palladium or a palladium-containing compound. Water is added either before or after the reaction is completed and the reaction products can easily be separated from the aqueous catalyst solution.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a process for telomerizing olefins, especiallydienes, with a telomerizing compound containing at least one mobilehydrogen atom, particularly to a process wherein the amount of the dieneis at least equivalent to the amount of mobile hydrogen atoms.

2. Description of the Prior Art

The French Pat. No. 2,045,369 discloses a process for preparingdiolefinic alcohols containing twice the number of carbon atoms of thestarting 1,3-diolefins. According to this process, a reaction mixture isformed containing the diolefin, water, and a solvent wherein thediolefin, as well as the water are at least partially soluble in thepresence of a catalyst containing palladium or platinum, phosphine andcarbon dioxide gas as a co-catalyst. The diolefinic alcohol is formed bythe reaction of the diolefin with water. For use in this type ofprocess, such solvents are selected which have a certain affinity forthe diene and for the water in order to maintain a liquid andhomogeneous reaction mixture. The solvents which are used are organicsolvents such as, e.g., dioxane, dimethyl acetamide, tert. butanol andacetone.

Processes for telomerizing diolefins, particularly butadiene, withvarious compounds containing mobile hydrogen atoms, such as alcohols,carbocyclic acids, silanols, ammonia, amines, compounds with reactivemethylene groups, and the like, in the presence of a catalyst usuallycontaining palladium and a co-catalyst, such as phosphine, are known inthe art [see Accounts Chem. Res., 1973, 6(1) 8-15].

The first major problem which arises during carrying out the prior artprocesses is the separation of the reaction products and the catalyst.It is, in effect, desirable to recover the catalyst for re-utilization.Yet the prior art proposes only processes wherein the final separationstep has never been satisfactorily solved by a generally applicablemethod. It proves always to be difficult and incomplete. In effect, inmost of the cases, not all of the reaction products can be separatedfrom the reaction medium by simple methods since on the one hand, thecatalyst is soluble in the organic solvents which are used and on theother hand, certain by-products are too non-volatile to be separated bydistillation. If it is possible to separate the main reaction product bydistillation, for reasons concerning the thermal stability of thecatalyst, it is impossible to eliminate the by-products, such as,oligomers and telomers of the diolefin, by distillation.

According to the prior art processes, a loss in catalyst is noted andthe latter is present in the reaction product.

In case the compound containing the mobile hydrogen atom is water, thesecond major problem is how to exalt its reactivity. The solutionsprovided by the prior art exist in, e.g., adding an alcohol to thereaction mixture (British Pat. No. 1,354,507 and U.S. Pat. No.3,670,032). A large amount of carbon dioxide gas has been used toincrease the reaction speed (French Pat. No. 2,045,369, cited above). Inthe first case, the major inconvenience is the joint formation ofundesirable ether (often even as the major product). In the second case,the amount of carbon dioxide has to be continuously recycled foreconomical reasons. Furthermore, the separation problems outlined aboveremain.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an improved processfor reacting a diene with a compound containing a mobile hydrogen, whichavoids these difficulties attendant the state of the art.

It is a further object of the present invention to provide such aprocess which permits an easy separation of the catalyst and thereaction products, e.g., by simple decantation or extraction, especiallya process which avoids the contamination of the reaction product withimpurities from the catalysts and avoids the loss of expensive catalyst.

It is a special object of the present invention to provide such aprocess wherein the catalyst can easily be recovered in a form which canbe directly re-used for the same reaction, e.g., which can be directlyrecycled into the reaction mixture.

In order to accomplish the foregoing objects according to the presentinvention there is provided a process for telomerizing dienes, whichcomprises the step of reacting a diene with a telomerizing compoundcontaining at least one mobile hydrogen atom in the presence of awater-soluble catalytic system comprising at least one water-solublephosphine having the formula (I) ##STR1## wherein Ar₁, Ar₂ and Ar₃ eachrepresent an aryl group having from 6 to 10 carbon atoms, which may bealike or different from each other; Y₁, Y₂ and Y₃, which may be alike ordifferent from each other each represent an alkyl group containing 1 to4 carbon atoms, an alkoxy group containing 1 to 4 carbon atoms, ahalogen, cyano-, nitro- or hydroxy radical or an ##STR2## wherein R₁ andR₂, which may be alike or different from each other each represent analkyl group containing 1 to 4 carbon atoms; M represents a cation whichis able to form water-soluble compounds of formula (I) selected from thegroup consisting of a proton, a cation derived from an alkali metal oran alkaline earth metal, ammonium, a group N(R₃ R₄ R₅ R₆)+ wherein R₃,R₄, R₅ and R₆ each represent hydrogen or an alkyl group containing 1 to4 carbon atoms and may be alike or different from each other, and acation of any other metal, which is able to form water-soluble saltswith benzosulfonic acids; m₁, m₂ and m₃ each represent a whole numberfrom 0 to 5 which may be the same or different from each other, and n₁,n₂ and n₃ each represent a whole number from 0 to 3, which may be thesame or different from each other, whereby at least one of these numbersn₁, n₂ and n₃ equals at least one and further comprising a compoundselected from the group consisting of a transition metal, preferablypalladium or a transition metal-containing compound, preferably apalladium containing compound.

Either before or after the reaction is completed, water is added to thereaction mixture, whereby an aqueous solution of the catalytic system isformed. When the reaction is finished, the reaction products can easilybe separated from the reaction mixture and a major portion of theaqueous solution of the catalyst can be recovered for re-use.

The process is preferably used for telomerizing dienes, especiallybutadiene and derivatives thereof into diene derivatives containing thedouble amount of carbon atoms than the starting materials. Yet, it canalso be used for tri- or tetramerization of dienes or for addition of amobile hydrogen containing compound to a diene molecule.

The ratio between the amount of diene and a telomerizing compound isequivalent to at least one molecule of diene per ten atom of mobilehydrogen.

Further objects, features and advantages of the present invention willbecome apparent from the following detailed description of the inventionand its preferred embodiment.

DETAILED DESCRIPTION OF THE INVENTION

Amongst the above-defined cations M, cations which are derived fromlead, zinc, or tin, can be cited as examples of cations which are ableto form water-soluble salts with benzosulfonic acids.

The process according to the present invention can be effected to eitherof the following two main embodiments.

According to the first embodiment, water is introduced before thetelomerizing reaction is completed. According to the second embodiment,water is introduced only after the telomerizing reaction is completed.

Within the first embodiment, two different cases have to bedistinguished. The first is related to the use of a mobilehydrogen-containing telomerizing compound which is sparingly soluble inwater; the other is related to the use of a water-soluble mobilehydrogen-containing telomerizing compound (e.g., the use of methanol).If the mobile hydrogen-containing compound is not water-soluble, twophases will be present at the end of the reaction: an aqueous phasecontaining the catalyst and an organic phase containing the reactionproducts. In this case, for example, the separation is done simply bydecantation or extraction. If the mobile hydrogen-containing compound isat least partially soluble in water, often only one single phase will bepresent at the end of the reaction. Then it is necessary to submit thisreaction mixture to a distillation operation in order to eliminate theremaining unreacted amount of the mobile hydrogen-containingtelomerizing compound, thereby obtaining a two-phase system of the kinddescribed above.

The aqueous phase which is recovered after decantation or extraction canbe directly recycled into the reaction. This permits one to carry outthe process in a continuous operation.

Within the second embodiment, water is added only after the reaction isterminated, and a system identical to that obtained at the end of thereaction in the first embodiment is obtained. In this embodiment, ofcourse, it will be necessary to eliminate the water again from thecatalyst in any conventional manner before recycling the latter into thereaction. This can be done, for example, by adding a heavy solvent whichpermits to deplete the water.

In the first embodiment, the phosphines can be introduced into thereaction mixture in the form of an aqueous solution.

Preferred are such phosphine compounds of formula (I) wherein Ar₁, Ar₂and Ar₃ each represent phenyl, Y₁, Y₂ and Y₃, which may be alike ordifferent from each other, each represent an alkyl group containing 1 to2 carbon atoms, an alkoxy group containing 1 to 2 carbon atoms orchlorine, M represent a proton, a cation derived from sodium, potassium,calcium or barium, ammonium, tetramethylammonium, tetraethylammonium,tetrapropylammonium or tetrabutylammonium; m₁, m₂ and m₃, which may bealike or different from each other, each represent a whole numberbetween 0 and 3.

Among those phosphines of formula (I), the most preferred are thesodium, potassium, calcium, barium, ammonium, tetramethylammonium andtetraethylammonium salts of (sulfophenyl)diphenylphosphine,di(sulfophenyl)phenylphosphine and tri(sulfophenyl)phosphine, whereinthe So₃ - groups preferably are situated in meta-position.

Further examples of phosphines of formula (I) which may be usedaccording to the process of the present invention are alkali metalsalts, alkaline earth metal salts, ammonium salts or quaternary ammoniumsalts of (m-sulfophenyl)diphenylphosphine,(p-sulfophenyl)diphenylphosphine,(m-sulfo-p-methylphenyl)di(p-methylphenyl)phosphine,(m-sulfo-p-methoxyphenyl)di(p-methoxyphenyl)phosphine,(m-sulfo-p-chlorophenyl)di(p-chlorophenyl)phosphine,di(m-sulfophenyl)phenylphosphine, di(p-sulfophenyl)phenylphosphine,di(m-sulfo-p-methylphenyl)(p-methylphenyl)phosphine,di(m-sulfo-p-methoxyphenyl)(p-methoxyphenyl)phosphine,di(m-sulfo-p-chlorophenyl)(p-chlorophenyl)phosphine,tri(m-sulfophenyl)phosphine, tri(p-sulfophenyl)phosphine,tri(m-sulfo-p-methylphenyl)phosphine,tri(m-sulfo-p-methoxyphenyl)phosphine,tri(m-sulfo-p-chlorophenyl)phosphine,(o-sulfo-p-methylphenyl)(m-sulfo-p-methyl(m,m'-disulfo-p-methyl)phosphine,(m-sulfophenyl)(m-sulfo-p-chlorophenyl)(m,m'-disulfo-p-chlorophenyl)phosphine.

As stated before, a mixture of these phosphines, particularly a mixtureof mono-, di-, or tri-metal-sulfonated phosphines can be used.

As a transition metal compound, preferably a palladium, nickel,platinum, cobalt or rhodium compound is used. Such compounds are usedwhich are water-soluble or able to be dissolved under the reactionconditions. The group which is connected to the transition metal is notcritical as long as these requirements are fulfilled.

These transition metals can also be used in the form of metals depositedonto an inert carrier, e.g., carbon black. Among the before-mentionedcompounds, palladium compounds are most preferred. The followingcompounds are cited as non-limiting examples: compounds wherein theredox value of the palladium is other than zero, e.g., palladiumacetate, carbonate, carboxylate, borate, bromide, chloride, citrate,hydroxides, iodide, nitrate, sulfate, arylsulfonates andalkylsulfonates, -acetylacetonate, bis(benzonitrile)palladium chloride,potassium tetrachloro palladate, and, π-allyl complexes of palladium,especially π-allyl palladium acetate or -chloride.

It is not necessary that the palladium compound as such be soluble inwater. For example, the palladium acetate is not very soluble in waterbut dissolves very well in an aqueous phosphine solution.

Among the compounds wherein the redox value of the palladium equalszero, a large number of various complexes can be used. The latter maycontain olefins, dienes, or cyano groups as a ligand. In particular,there can be used tetra(biphenyl)phosphine palladium (zero),bis(cyclo-octadiene-1,5) palladium (zero) or potassium tetracyanopalladate. In this latter case, the compound may be dissolved in anon-water miscible solvent like toluene. An aqeous solution of asulfonated phosphine extracts part of the palladium therefrom, whereby ayellow coloration develops in the decanted aqueous solution.

Finally, palladium metal deposited onto an inert support such as carbonblack can also be used.

The amount of transition metal compounds, especially palladiumcompounds, which are used are chosen in such a range that the reactionsolution contains between about 10⁻⁴ and about 1 gram atoms, preferablybetween about 0.005 and 0.5 gram atoms of elementary metal per liter.

The amount of phosphine compounds of formula (I), which is used withinthe reaction medium is chosen in the range that the reaction mediumcontains between about 1 to about 2,000, preferably between about 1 and3 moles of phosphines per gram atom of elementary metal.

Even so, this is not absolutely necessary when palladium metal or one ofthe above-mentioned palladium compounds are used, a palladium reducingagent, preferably a palladium reducing agent which reacts with thepalladium under the given reaction conditions, is added to the reactionmedium. This reducing agent may be an organic or inorganic agent. Thefollowing agents are cited as non-limiting examples: sodium borohydride,powdered zinc, magnesium, potassium borohydride and other boronhydrides, preferably water-soluble boron hydrides.

It is advisable to add an amount of reducing agent which corresponds tobetween about 1 and about 10 redox equivalents. Nevertheless, theaddition of lower amounts or higher amounts which correspond to morethan 10 redox equivalents is not excluded.

Such a reducing agent may also be added if platinum or rhodium are used.If nickel or cobalt are used, the use of a reducing agent is necessarywhen their redox value is other than zero, but not imperative if theredox value equals zero. The same reducing agents which are used withpalladium can be used.

The sulfonated phosphines which are used within the process of thepresent invention can be prepared by conventional methods. Thus,according to the teachings of H. Schindlebauer, Monatsch. Chem., 96,pages 2051-2057 (1965), the sodium salt of(p-sulfophenyl)-diphenylphosphine can be prepared by reacting sodiump-chlorobenzene sulfonate with diphenylchlorophosphine in the presenceof sodium or potassium. According to the method which is described in J.Chem. Soc., pp. 276-288 (1958), and in the British Pat. No. 1,066,261,phenylphosphines of formula (I) can be prepared by using the method ofsulfonating aromatic nuclei by means of oleum and then neutralizing theformed sulfonic groups by means of an appropriate basic derivative ofone of the metals, which are represented by M in the formula (I). Thecrude sulfonated phosphines which are obtained may contain correspondingoxides of sulfonated phosphines mixed with them, yet the presencethereof does not interfere with performing the hydroxyanation processaccording to the present invention.

The process of the present invention is suited for telomerizing olefins,preferably aliphatic dienes, which contain 4 to 20, preferably 4 to 8,carbon atoms and may be substituted by lower alkyl groups. Inparticular, lower aliphatic conjugated dienes, such as, butadiene,isoprene, piperylene or dimethylbutadiene are treated according to theprocess of the present invention.

A telomerizing compound containing at least one mobile hydrogen atom isa compound which contains at least one reactive hydrogen atom. Thefollowing groups of compounds may be cited as examples of compoundscontaining reactive hydrogen atoms: water, alcohols, phenols, acids,amines, silanols or compounds containing a reactive methylene group.

Among the alcohols, the following may be cited as suitable examples:primary, aliphatic, saturated, branched or straight alcohols containingpreferably 1 to 8 carbon atoms, such as, methanol, butanol and the like,unsaturated aliphatic alcohols containing preferably 3 to 8 carbonatoms, such as, allyl alcohol, saturated aliphatic or alicyclicsecondary alcohols containing preferably 3 to 8 carbon atoms such asisopropanol or cyclohexanol, aromatic alcohols containing 7 to 12 carbonatoms, such as, benzyl alcohols, fluorinated aliphatic or aromaticalcohols, e.g., tertiary alcohols of the formula ##STR3## wherein Arrepresents an aryl group containing 6 to 10 carbon atoms, preferablyphenyl or benzyl, or alcohols of the formula CF₃ --(CF₂)_(n) --CH₂ OH,wherein n is an integer from 1 to 6, or polyols preferably containing 2to 8 carbon atoms, e.g., glycol.

Among the phenols, unsubstituted phenols and phenols substituted bylower alkyl, lower alkoxy, or halogen are particularly suited. Asexamples, there may be cited phenol p-chlorophenol, o-methoxyphenol,dimethylphenols and cresols.

Among the acids, lower aliphatic and aromatic mono- or divalent acids,preferably containing less than 12 carbon atoms are particularly suited.As examples, there may be cited aliphatic monocarboxylic acids, such asacetic acid, aliphatic dicarboxylic acids, such as adipic acid, aromaticmono- or dicarboxylic acids, such as benzoic acid or o-phthalic acid.

Among the amines which can be used within the process according to thepresent invention, primary aliphatic or aromatic amines, e.g., loweralkyl amines, such as methylamine or aniline, secondary aliphatic oraromatic amines, e.g., di(lower alkyl) amines, such as diethylamine,lower alkyl anilines, such as methyl aniline, heterocyclic amines,preferably containing 5 or 6 ring members, e.g., piperidine ormorpholine. Ammonia can also be used.

Among the compounds containing a reactive methylene group acetonederivatives, e.g., lower aliphatic or aromatic acyl or carboxylderivatives of acetone are particularly suited. The following may becited as examples: acetylacetone, benzoylacetone, ethyl acetoacetate.Also suited are nitro compounds e.g., nitro-methane.

By reacting 2 moles of diene, e.g., butadiene, with one mole of one ofthe various compounds HX_('), the following compounds are obtained:##STR4## wherein X_(') is: ##STR5## wherein 2 is alkyl or aryl and Y isalkyl, aryl or alkoxy.

By reacting one mole of butadiene with one mole of a compound HX_("),wherein X_(") is --Oφ_(') --OCOCH₃ or NR₂, the following compounds areobtained: ##STR6##

In the case that the mobile hydrogen-containing compounds include morethan one mobile hydrogen atom per molecule, a replacement of all themobile hydrogen atoms can be obtained. Thus, starting from butadiene andan amine RNH₂ dioctadienyl alkyl- or aryl amines of the ##STR7## areobtained.

According to the present invention, the following compounds areprepared:

1-methoxy-2,6-dimethyloctadiene-2,7 starting from 1-isoprene andmethanol

octadiene-2,7-ol-1 starting from butadiene and water

1-acetocyoctadiene-2,7 starting from butadiene and acetic acid

1-phenoxyoctadiene-2,7 starting from butadiene and phenol

N,n-diethylamino-1-octadiene-2,7 and N,N-diethylamino-1-butene-2starting from butadiene and diethylamine

N-octadienyl-2,7-morpholine starting from butadiene and morpholine.

The compounds which are obtained according to the present invention areuseful as intermediates for the synthesis of plasticizers, plasticmaterials, perfumes, pharmaceuticals and galvano plastics.

The process according to the present invention may be effected in thepresence of further additives. Suitable additives are bases, such ashydroxides of alkali metals, alkaline earth metals, tertiary aliphaticor aromatic amines, phenolates, or solutions corresponding to mixturesof the beforementioned bases and acids, such as, for example, mineralacids of elements of the Group IIIA, such as, boric acid, acids ofelements of the Group IVA, such as, carbonic acid, acids of elements ofthe Group VA, such as, phosphoric acid and acids of tri- or five valentphosphorous, or arsenic acid, acids of elements of the Group VIA, suchas, sulfuric acid, sulfurous acid or alkylsulfonic acid, acids ofelements of the Group VIIA such as hydrofluoric acid, hydrochloric acid,hydrobromic acid, or hydroiodic acid, organic acids such astrifluoromethane sulfonic acid, trifluoroacetic acid, aryl- oralkylsulfonic acids, carboxylic acids such as, acetic acid and weakacids like phenol.

For each mobile hydrogen containing compound, the person skilled in theart can choose the appropriate combination of the above-mentionedadditives in order to achieve the best reaction speed and to facilitatethe recycling.

Due to its low reactivity, water will not chemically interfere as areactant in the case where it is used as a solvent for the catalyst. Ithas been found that when water is used as a mobile hydrogen-containingreactant, the addition of certain water-soluble compounds significantlyincreases the reaction speed. Among these compounds are alkalineelectrolytes, alkali carbonates and -bicarbonates, such as, sodiumcarbonate and -bicarbonate, sodium silicates and alkaline salts ofphosphorous phosphoric and arsenic acids.

It may be advisable to add to the reaction mixture an organic solventwhich is inert towards the various components of the reaction mixture.There can be used a solvent which is immiscible with water or a solventwhich is miscible with water. In the latter case, the solubility of,e.g., the butadiene in water increases and the reaction speed can beincreased. Solvents which are immiscible with water provide for a betterdecantation.

The following are cited as examples for water miscible solvents:acetone, acetonitrile, dimethylether or diethylene glycol,dimethoxyethane, dioxane, tert. butanol, dimethyl acetamide, n-methylpyrolidone and ethylene carbonate, dimethoxyethane, and as examples ofimmiscible solvents, benzene, benzonitrile, acetophenone, isopropylether, octane, methylethylacetone and propionitrile can be mentioned.

The temperature at which the reaction is performed may vary within wideranges. Moderate temperatures between -20° to 200° C., preferablytemperatures between about 20° and about 125° C., are particularlysuitable.

According to an embodiment of the process of this invention, anappropriate reaction vessel, which has been purged by means of an inertgas (nitrogen or argon) is charged either with an aqueous catalyticsolution which was prepared before or with the various components: aphosphine, water, the transition metal compound optionally together witha reducing agent, an additive, and an organic solvent. The reactionvessel is brought to the reaction temperature before or after the mobilehydrogen-containing compound is introduced, which itself may beintroduced before, after or simultaneously with the diene.

After stopping the reaction, the mixture is cooled to room temperature.The content of the reaction vessel is drawn from the vessel, andafterwards, the reaction product has only to be recovered by subsequentdecantation or eventually by extraction by means of appropriate solventssuch as, e.g., the water immiscible solvents which were cited above.

The remaining aqueous solution may be recycled into the reaction vesselfor catalyzing a new reaction. The aqueous solution may also stay in thereaction vessel when the organic compounds are drawn from it.

Another embodiment of the process according to the present inventioncomprises carrying out the above operation but introducing the wateronly after the reaction as such has stopped. In this case, beforerecycling the catalyst, the water has to be eliminated again by anyconvenient means.

It was found that the process according to the present invention allowsto obtain yields which depending on the respective reaction can be ashigh as 95%.

The following examples are intended only to further illustrate theinvention without limiting it.

EXAMPLE 1

Into a 500 ml stainless steel autoclave which was equipped with aknock-type agitation system, the following were introduced:

40 g of a solution containing:

0.0178 g (0.1 m mole) of palladium chloride and

0.124 g (0.3 m mole) of the mono sodium salt of(m-sulfophenyl)diphenylphosphine dihydrate content in trivalentphosphorus 95% of the theoretical amount) in methanol.

40 g of additional methanol

0.100 g (1.8 m mole) of potash

0.030 g (1 m mole) of sodium borohydride

The autoclave was purged for 30 minutes with argon, then 25 g ofbutadiene were introduced. The autoclave was than agitated for 21 hoursat 30° C. Then also at 30° C., 4 g of butadiene were degassed. Thereaction mixture was transferred into a distillation apparatus. It wascomposed of one yellow limpid phase. Butadiene and methanol were removedby distillation at a pressure of 100 mm mercury by heating the flask upto 33° C. and adding water. The concentrated reaction mixture containedtwo phases:

7.9 g of an aqueous phase of yellow color containing the catalyticsystem

a colorless organic phase comprising mainly the methoxy octadienes.

According to chromatographical analysis, the following results wereobtained by the above procedure:

percentage of conversion of the butadiene: 56%

yields per amount of used up butadiene:

    ______________________________________                                        1-MOD: 95%         MOD = methoxyoctadiene                                     3-MOD:  4%                                                                    C.sub.8 :                                                                            traces of   C.sub.8 = other hydrocarbon compounds                             less than 1%                                                                              containing 8 carbon atoms                                                     per molecule                                               ______________________________________                                    

The catalytic system was in the aqueous phase.

EXAMPLE 2

Into a 500 ml stainless steel autoclave which was equipped with aknock-type agitation system, the following were introduced:

0.224 g (1 m mole) of palladium acetate

0.464 g (4 m mole) of sodium phenolate

2 g (3.9 m mole) of the mono sodium salt of (m-sulfophenyl)diphenylphosphine dihydrate (content in trivalent phosphorus 80% of thetheoretical amount)

15 ml of water

78.6 g of methanol

This was purged for 30 minutes with argon, then 70 g of butadiene wasintroduced. The autoclave was then agitated at 95° C. for 18 hours andthen cooled to 50° C. in order to eliminate the unreacted butadiene(less than 2 g). Then at 35° C. and under argon, the content of theautoclave was transfered into a conical distillation apparatus throughwhich argon was passed. The reaction mixture comprised two phases.Methanol was removed by distillation. The distillation was carried outat atmospheric pressure by heating the boiler to 101° C., whereby thetemperature at the top of the column was 90.5° C. During thedistillation, 10 ml of water were added in order to obtain an aqueousphase the volume of which was between about 15 and 30 ml. This aqueousphase, which contained the catalyst, was recycled into the autoclaveunder argon. The supernatant organic phase, the weight of which was 75.6g, comprised mainly methoxyoctadienes.

According to chromatographical analysis, the following results wereobtained by the above procedure:

percentage of conversion of the butadiene: >95%

yields per amount of used up butadiene:

1-MOD: 78%

3-MOD: 7%

C₈ : 11%

The remainder to 100% was comprised of mainly oligomers and telomers.

EXAMPLE 3

Into a 125 ml stainless steel autoclave, which was equipped with aknock-type agitation system, the following were introduced:

0.039 g of palladium acetate

0.958 g of the tetramethylammonium salt of tri(m-sulfophenyl) phosphine(purity 60%)

8.5 g of methanol.

The autoclave was purged for 30 minutes with argon then 10.5 g ofbutadiene were introduced. The autoclave was then agitated for 16 hoursat 95° C. The autoclave was cooled, then the reaction products weredistilled at a pressure of 0.1 mm mercury by heating the autoclave to80° C.

With the catalytic system which remained in the autoclave the sameoperation was repeated three times using the following reactants:

2nd operation -- 25 g of butadiene, 23 g of methanol;

3rd operation -- 21 g of butadiene, 24 g of methanol;

4th operation -- 24 g of butadiene, 25 g of methanol.

According to the analytical data, the percentage of conversion of thebutadiene was 100% and it was transformed into:

dimer hydrocarbons 20%, mainly octatriene-1,3,7.

1-MOD: 59% - 3-MOD: 10% - heavy products: 11%

The catalytic system was separated from the heavy products by addingwater and decanting.

EXAMPLES 4, 5 and 6

Into a 125 ml stainless steel autoclave which was equipped with aknock-type agitation system, tests with different phosphines werecarried out. After introducing the reactants and the catalytic systemand allowing the reaction to take place for 18 hours at 95° C., theseparation of the catalytic system was effected by adding water. Theresults are shown in the Table below:

Example 4: tetraethylammonium salt of tri(m-sulfophenyl) phosphine(purity: 60% determined as trivalent phosphorus)

Example 5: monosodium salt of (m-sulfophenyl)diphenyl phosphinedehydrate (purity 85%).

Example 6: disodium salt of di(m-sulfophenyl)phenyl phosphine (purity100%, determined as trivalent phosphorus). Amound of methanol: 20 ml,amount of butadiene: 20 ml.

    ______________________________________                                                            Con-                                                      Weight of           version                                                   the        Pd(oAc).sub.2                                                                          of       Selectivity %                                    Ex.  ligand(g) mg       butadiene                                                                            1-MOD  3-MOD  C.sub.8                          ______________________________________                                        4    0.96      39       100    70     14     11                               5    0.32      34       90     83     7       9                               6    0.35      38       83     78     8      11                               ______________________________________                                    

With the mono sodium salt of (p-sulfophenyl)diphenylphosphine preparedaccording to Schindlbauer, essentially the same results were obtained.

EXAMPLE 7

Into a 125 ml stainless steel autoclave which is equipped with aknock-type agitation system, the following were introduced:

0.135 g of palladium acetate (0.6 m mole)

1.61 g of trisodium salt of tri(m-sulfophenyl)phosphine (purity 90%)(2.4 m mole) (TPPS)

10.8 ml of water

1.38 g of potassium carbonate (10 m moles), that is a concentration ofone mole/l water.

The autoclave was purged for 30 minutes with argon, then 18 g ofbutadiene were added. Then the autoclave was agitated for 3 hours at 80°C., then cooled to 60° C. for eliminating the major portion of unreactedbutadiene by degassing. After cooling to 20° C., and opening theautoclave, a reaction mixture comprising two layers were removed into adecantor. The two layers were:

an aqueous layer (10.6 g) containing the catalytic system

an organic layer (11.8 g) containing the following components accordingto chromatographical analysis:

10% of C₈ -- hydrocarbons mainly octatriene-1,3,7

63% of octadiene-2,7-ol-1 (=ol-1)

21% of octadiene-1,7-ol-3 (=ol-3)

The remainder to 100% comprises mainly butadiene and heavier productsthan octadienols. The aqueous layer is used for carrying out further newoperations.

EXAMPLES 8-16

According to the method described in Example 7, a certain number oftests were carried out adding different co-catalysts to the water. Theresults demonstrate well the necessity of finding out the appropriatecombinations of acids and bases for each telomerization reaction inorder to obtain the best results. For example, palladium in an aqueoussolution of sulfonated phosphine is not very active in catalyzing theaddition of water; on the contrary, adding carbonate, bicarbonate,phosphate, phosphites, silicates or arsenates, permits to markedlyaccelerate the reaction.

                                      TABLE                                       __________________________________________________________________________                                  Results per amount of butadiene                 Charges                       Percentages          Level of                              Palladium          of          Yields                                                                            Yields                                                                             catalysis                  Examples                                                                           Butadiene                                                                           acetate                                                                              Phosphine                                                                           Additives                                                                           conversion                                                                           C.sub.8                                                                            1-ol                                                                              3-ol (1)                        __________________________________________________________________________     8   22 g  0.135 g                                                                              1.6 g         1.3% 66%  28%  6%  4.5                                   0.6 m mole                                                                           2.4 m mole                                                   9   18 g  "      "     K.sub.2 CO.sub.3                                                                    71%    10%  63% 21%  202                                                1.38 g                                                                        1 mol/l                                               10   19 g  "      1.22 g                                                                              "     76%    12%  64% 20%  229                                          1.8 m mole                                                  11     16.2 g                                                                            "      "     KH CO.sub.3                                                                         35%     9%  78% 13%  90                                                 1 g                                                                           1 mol/l                                               12   20 g  0.0337 g                                                                             0.4 g K.sub.2 CO.sub.3                                                                    13%      6.5%                                                                             71% 22%  162.5                                 0.15 m mole                                                                          0.6 m mole                                                                          1 mol/l                                               13   23 g  "      "     H.sub.3 PO.sub.4                                                                     9%    25%  62%   12.3%                                                                            129                                                1 mol/l                                                                       NaOH                                                                          2.5 mol/l                                             14   28 g  "      "     H.sub.3 PO.sub.3                                                                      14.5%                                                                              16.9%                                                                              58% 21%  254                                                1 mol/l                                                                       NaOH                                                                          2.5 mol/l                                             15   13 g  0.0337 g                                                                             0.4 g Na.sub.2 H AsO.sub.4                                                                 8%    24%  56% 15%  65                                    0.15 m mole                                                                          0.6 m mole                                                                          1 mol/l                                                                       NaOH                                                                          0.5 mol/l                                             16   18 g  "      "     Sodium                                                                              24%    16%  68% 15%  270                                                Silicate (2)                                          __________________________________________________________________________     (1) The level of catalysis was determined as the ratio between the weight     of butadiene which had reacted and the weight of the palladium which was      applied.                                                                      (2) 5 ml of an aqueous solution having a density of 1.3 (sold by Societe      PROLABO)                                                                 

EXAMPLES 17 AND 18

Into a 125 ml stainless steel autoclave purged with argon and equippedwith a knock-type agitation system, the following were introduced:

    ______________________________________                                                                    Sodium                                            Wa-                         Pheno-       Buta-                                ter      TPPS    Salt       late   Phenol                                                                              diene                                ______________________________________                                        Ex.17 10.8    2.4    Pd(oAc).sub.2                                                                          1.25 g 18.8 g                                                                              23 g                                     cm3    m mole   0.6 m mole                                                                            1 mole/l                                        Ex.18 10.8   1.36    PtCl.sub.2                                                                             1.25 g 18.8 g                                                                              23 g                                     cm3    m mole  0.45 m mole                                                                            1 mole/l                                        ______________________________________                                    

The autoclave was then agitated for 3 hours at 80° C. then cooled to 60°C. in order to eliminate the major portion of the unreacted butadiene.After cooling to 20° C. and opening of the autoclave, the reactionmixture comprising two layers were recovered into a decantor. The upperphase contained the organic products, the below aqueous phase containedthe catalyst and sodium phenolate. According to the analysis, thepercentage of conversion and the yields were as follows:

    ______________________________________                                                             Ex. 17 Ex. 18                                            ______________________________________                                        Percentage conversion of butadiene                                                                   90%      40%                                           Yield in hydrocarbons C.sub.8                                                                        18%       5.5%                                         Yield in 1-phenoxybutene-2                                                                            1%      18.5%                                         Yield in 3-phenoxybutene-1                                                                             0.8%   18.5%                                         Yield in 3-phenoxyoctadiene-1,7                                                                      21%       4.46%                                        Yield in 1-phenoxyoctadiene-2,7                                                                      56%      46.2%                                         ______________________________________                                    

EXAMPLE 19

Into a 125 ml stainless steel autoclave purged with argon and equippedwith a knock-type agitation system, the following were charged:

10.8 g water

1.83 g trisodium salt of tri(m-sulfophenyl)phosphine (purity 90%)

0.135 g of palladium acetate

14.6 g of diethylamine

19 g of butadiene.

The autoclave was then agitated during 3 hours at 85° C., then cooled to60° C. in order to eliminate a portion of the unreacted butadiene. Thereaction mixture formed two distinct immiscible layers which weredecanted. The aqueous layer containing the catalyst weighed 12.5 g. Thecolorless organic layer weighed 26 g, it contained:

13.5% of butadiene

46.5% of 1-(N,N-diethylamino)butene-2

40% of 1-(N,N-diethylamino)octadiene-2,7

0.6% of 3-(N,N-diethylamino)octadiene-1,7

EXAMPLE 20

Into a 125 ml stainless steel autoclave purged with argon and equippedwith a knock-type agitation system, the following were introduced:

12 g of acetic acid

17.8 g of dimethylamino-2-ethanol

0.33 g of tetraethylammonium salt of tri(m-sulfophenyl) phosphine(purity 90%)

0.050 g of palladium acetylacetonate

10.5 g of butadiene

The autoclave was then agitated for two hours at 90° C., then cooled to60° C. in order to eliminate a porton of the unreacted butadiene. Thereaction mixture was distilled. The catalytic system was separated fromthe heavy products by adding water and decanting. According to theanalysis of the distillates, the percentage of conversion of thebutadiene was 94%, namely 56% of 1-acetoxyoctadiene-2,7 and 36% of dimerhydrocarbons that is octatriene-1,3,7.

EXAMPLE 21

Into a conical 250 ml flask purged with argon, the following wereintroduced:

80.8 g of methanol

0.330 g of mono sodium salt of (m-sulfophenyl)diphenylphosphine, (purity97%)

0.045 g of palladium acetate

0.6 g of potash

0.035 g of sodium borohydride

28 g of isoprene.

The homogeneous mixture was agitated for 68 hours at 45° C. The mixturewas cooled and 60 ml of water and 0.33 g of phosphine were added, thenmethanol and isoprene were removed from the boiler by heating them to36° C. under a pressure of 100 mm of mercury. The supernatant organiccolorless phase weighed 21 g and contained 70% ofmethoxy-1-dimethyl-2,6-octadiene-2,7, the remainder to 100% consistingof dimer hydrocarbons, as isomer and heavier products. The aqueous phasecontained the catalytic system.

EXAMPLE 22

Into a 125 ml stainless steel autoclave purged with argon and equippedwith a knock-type agitation system, the following were introduced:

20 ml of methanol

0.45 g of sodium salt of (m-sulfophenyl)bis(phenyl)phosphine, (purity97%)

0.5 g of palladium on carbon black 10%

19 g of butadiene

The mixture was then agitated during 3 hours at 85° C., then cooled to60° C. in order to eliminate a portion of the unreacted butadiene. Thereaction mixture was filtered in order to eliminate the carbon blacktherein. The organic phase contained unreacted methanol and:

15 g of methoxy-1-octadiene-2,7

0.75 g of methoxy-3-octadiene-1,7

0.75 g of a dimer of butadiene

The catalyst can be separated from the reaction mixture as described inExample 2.

EXAMPLE 23

Into a 10 ml glass tube, the following were introduced under argonatmosphere:

0.679 g of mono sodium salt of (m-sulfophenyl)diphenylphosphine, (purity97%)

5 ml of ethanol.

The tube was cooled to -78° C. and then were introduced:

0.107 g of anhydrous nickel chloride

0.27 g of butadiene

0.123 g of sodium borohydride

The glass tube was then isolated and closed by means of a Bakelite screwclosure which comprised a rubber insert which allowed the injection ofliquids by means of a syringe.

The mixture was allowed to warm up to -40° C. 1.36 g of butadiene and0.8 ml of morpholine were added. The reaction mixture was reheated to20° C. and maintained at 20° C. for 1 hour and 30 minutes. According tochromatographical analysis, the percentage of conversion of morpholinewas above 95% with a yield of 90% of N-octadienylmorpholine. The ethanolwas removed by distillation. The catalyst was separated from thereaction products by adding water.

PREPARATION OF THE PHOSPHINES WHICH WERE USED IN THE EXAMPLES

(1) preparation of the sodium salt of (metasulfophenyl)diphenylphosphine

This phosphine was prepared according to the preparation method, whichis described by S. Ahrland, J. Chatt, N. R. Davies, A. A. Williams,Journal of Chemical Society, 276-288 (1958).

(2) Preparation of the sodium salt of (p-sulfophenyl)diphenylphosphine

This phosphine was prepared according to the preparation methoddescribed by H. Schindlbauer, Monatsch. Chem., 96, pp. 2051-2057 (1965)by reacting sodium p-chlorobenzene sulfonate withdiphenylchlorophosphine in the presence of sodium.

(3) Preparation of the sodium salt of tri-(metasulfophenyl)phosphine

Into a 2 liter balloon flask which was equipped with a central stirringsystem, a thermometer and an ascendent cooler and which was cooled fromthe outside by an ice water bath, there was introduced a liter of oleumcontaining 20% by weight of sulfuric anhydride, then the flask waspurged with argon. The stirring was started, subsequently 100 g oftriphenylphosphine were introduced within 2 hours thereby keeping thetemperature between 20° and 40° C. When the addition was finished,stirring of the mixture was continued at the above temperature during 15to 25 hours. The reaction was then cooled to 10° C. and was carefullypoured into a 10 liter balloon flask which contains 2 liters of waterwhich was cooled to 0° C. 1,500 g of sodium hydroxide pastils were addedto the reaction mixture, whereby the temperature of the reaction mediumwas maintained at below 20° C. The resulting solution was allowed tostand for several hours at room temperature, at about 20° C.

At the end of this period, the precipitated sodium salts were recoveredby filtration and washed twice with 1,500 ml of ice water each. Thecombined filtrates and washing waters were concentrated to a totalvolume of 1,500 ml by heating at reduced pressure.

The precipitate which was obtained at the end of the concentratingoperation was filtered and washed three time with 300 ml ice water each.The combined filtrate and washing waters were concentrated to a volumeof 500 ml by heating under reduced pressure.

To the mixture remaining from the above concentration step, 500 ml ofmethanol were added, then the forming precipitate was filtered andwashed with 500 ml of a mixture of methanol/water 50/50. The combinedfiltrate and washing solutions were then concentrated to a volume of 200ml, then 1,000 ml of methanol were added. The precipitate which wasformed was filtered, then washed six times with 1,000 ml of methanolheated to 60° C. The molten liquors and washing solution were combinedand evaporated to dryness. The evaporation residue was introduced into500 ml of absolute ethanol. The resulting solution was filtered and thesolids on the filter were washed with 20 ml of ethanol and then dried at25° C. under reduced pressure (0.1 mm mercury) during 30 hours. 172 g ofa white solid remain.

The results of analyzing the solid product by elementary analysis(determination of the content in C, H, S, P) by infra red spectroscopyby nuclear magnetic resonance of hydrogen and phosphorus and by chemicaldetermination of the trivalent phosphorus (iodometric determination),and the sulfonated groups by ion exchange indicated that the product wasa mixture of tri sodium salts of tri(metasulfophenyl)phosphine and oftri(metasulfophenyl)phosphine oxide.

The composition of the mixture of salts may vary according to thetemperature and the reaction time of the sulfonation. When the additionof the triphenylphosphine is effected at a temperature of about 30° C.,and agitating of the mixture is continued at this temperature for about20 hours, a mixture is recovered wherein 80% by weight of the salts inthe solution are sodium salts of tri(metasulfophenyl)phosphine and 20%by weight are sodium salts of tri(metasulfophenyl)phosphine oxide. Whenworking at 40° C. for 24 hours, the obtained mixture of salts contains60% by weight of the sodium salt of the tri(metasulfophenyl)phosphine.

By carrying out the reaction at 18°-20° C. during 48 hours a producthaving a purity of above 95% is obtained.

(4) Preparation of an ammonium salt of tri(metasulfophenyl)phosphine

A suitable amount of the sodium salt of tri(m-sulfophenyl)phosphinewhich was prepared as described above, was dissolved in water and thesolution was passed through a column which contained an excess (about 4times the theoretical amount) of a strongly acid ion exchange resin(sulfonic acid) which is known under the tradename Amberlite IR 120H,finally was eluated with water. The resulting acid solution wasneutralized with tetraethylammonium hydroxide and then was evaporated todryness under reduced pressure.

All triphenylphosphine salts can be prepared according to the sameprocedure.

(5) Preparation of the sodium salt of di(metasulfophenyl)phosphine

This phosphine is obtained by the following reaction. Into an 0.5 literballoon flask which was equipped with a central stirring system, athermometer and an ascendent cooler and which was cooled from theoutside by an ice water bath, there were introduced 100 ml of oleumcontaining 20% by weight of sulfuric anhydride, then the flask waspurged with argon. The stirring was started, subsequently 10 g oftriphenylphosphine were introduced thereby keeping the temperature at25° C. Stirring of the mixture was continued at this temperature during17 hours. The reaction mixture was poured into a flask which contained1,000 g of ice then the mixture was neutralized by means of 400 ml of anaqueous 10 N sodium hydroxide solution.

The precipitated salts were filtered and then dried to constant weight.18 g of a solid was obtained and was introduced into 65 ml of water,which was heated to boiling. The insoluble particles were separated byhot filtration and the filtrate was left to cool to 20° C. Theprecipitated solid was separated by filtration, washed with 10 ml ofcold water, then dried at 25° C. under a pressure of 0.1 mm mercuryduring 30 hours. Thus, 8 g of the disodium salt of puredi(m-sulfophenyl)phosphine were recovered.

EXAMPLE 24

A test was carried out analogous to Example 12, but replacing thepotassium carbonate by 1.64 g of sodium phenyl sulphinate (i.e., aconcentration of 1 mole per liter). The degree of conversion of thebutadiene was 55%. The supernatant organic phase contained hydrocarbondimers of butadiene (yield 9.7%), of 2-trans,7-octadiene-1-ol (yield62%) and of 1,7-octadiene-3-ol (yield 16%).

EXAMPLE 25

In a 125 cm³ stainless steel autoclave equipped with a shaker wereintroduced:

0.040 g of platinum chloride (PtCl₂)

0.38 g of the trisodium salt of tri(meta-sulphophenyl)phosphine (purity95%)

10.8 cm³ of water

13.8 g of diethylamine.

The autoclave was purged for 30 minutes with argon and then 18 g ofbutadiene were introduced. The autoclave was then agitated for 3 hoursat 80° C. and then cooled to 60° C. in order to remove the bulk of thebutadiene which had not reacted, by degassing. After cooling to 20° C.and opening the autoclave, a reaction mixture, which consisted of thefollowing two layers, was collected in a decanter:

an aqueous layer (9.1 g) containing the catalytic system

an organic layer (15.6 g) containing part of the reactants which had notreacted and 3.99 g of 1-diethylamino-2-trans-butene as the sole reactionproduct.

EXAMPLE 26

Following the procedure of Example 25, an experiment was carried outwith the following materials:

0.036 g of [RhCl(cycloocta-1,5-diene)]₂

0.114 g of trisodium salt of tri(m-sulfophenyl)phosphine (purity 95%)

10.8 cm³ of water

14.8 g of diethylamine, and

19 g of butadiene.

The degree of conversion of the butadiene was about 10%. It had beenconverted into 1-diethylamino-2-trans-butene (23%) and1-N-diethylamino-2-trans,7-octadiene.

EXAMPLE 27

When a taxogen, such as diethylamine is used, the addition of acid caneffect the selectivity. For example, by following the procedure ofExample 19, but adding 0.024 mole of sulphuric acid a reaction mixturewas obtained containing, by mole:

13.9% of C₈ hydrocarbon

64.4% of 1-N-diethylamino-2,7-octadiene

13.9% of octadienol.

The absence of 1-diethylamino-2-trans-butene is noted.

EXAMPLE 28

The following constituents were introduced into a 125 cm³ stainlesssteel autoclave fitted with a shaker:

0.107 g of platinum chloride (PtCl₂)

0.815 g of trisodium salt of tri(m-sulfophenyl)phosphine (purity 95%)

10.8 g of water

14.6 g of diethylamine

20 g of isoprene.

The autoclave was then agitated for 20 hours at 80° C. After cooling,32.2 g of an organic phase were decanted. The degree of conversion ofthe amine was about 93%, it had been converted into:

1-N-diethylamino-2-methyl-2-trans-butene (24%).

1-N-diethylamino-3-methyl-2-trans-butene (72%).

The process according to the present invention is preferably suited forreacting a sufficient amount of a compound of formula (II) ##STR8##containing 4 to about 20 carbon atoms, wherein at least one of thesubstituents R₁, R₂, R₃, R₄ and R₅ is hydrogen and the remainingsubstituents R₁, R₂, R₃, R₄ and R₅ are the same or different and eachrepresent hydrogen, alkyl having 1 to 5 carbon atoms or alkenyl having 3to 5 carbon atoms, with a telomerizing compound HOR, wherein Rrepresents hydrogen, alkyl having 1 to about 20 carbon atoms, alkenylhaving 3 to about 20 carbon atoms, aryl having 6 to about 20 carbonatoms, or an ##STR9## wherein R₆ and R₇ are the same or different andeach are hydrogen, alkyl having 1 to 20 carbon atoms or alkenyl having 3to 20 carbon atoms or R₆ and R₇ together with the nitrogen atom form a5- or 6-membered heterocyclus to form a reaction product containing amajor portion of dimer derivatives of the compound of formula (II).

While the invention has now been described in terms of various preferredembodiments, and exemplified with respect thereto, the skilled artisanwill appreciate that various substitutions, changes, omissions, andmodifications may be made without departing from the spirit thereof.Accordingly, it is intended that the scope of the invention be limitedsolely by that of the following claims.

What is claimed is:
 1. A process for telomerizing dienes which comprisesthe step of reacting a diene with a telomerizing compound containing atleast one mobile hydrogen atom, said telomerizing compound being water,in the presence of a water-soluble catalytic system comprising at leastone water-soluble phosphine having the following formula (I): ##STR10##wherein Ar₁, Ar₂ and Ar₃ each represent an aryl group having from 6 to10 carbon atoms, which may be alike or different from each other; Y₁, Y₂and Y₃, which may be alike or different from each other each representan alkyl group containing 1 to 4 carbon atoms, an alkoxy groupcontaining 1 to 4 carbon atoms, a halogen, cyano-, nitro-, or hydroxyradical or an ##STR11## wherein R₁ and R₂, which may be alike ordifferent from each other each represent an alkyl group containing 1 to4 carbon atoms; M represents a cation which is able to formwater-soluble compounds of formula (I) selected from the groupconsisting of a proton, a cation derived from an alkali metal or analkaline earth metal, ammonium, a group N(R₃ R₄ R₅ R₆)+, wherein R₃, R₄,R₅ and R₆ each represent hydrogen or an alkyl group containing 1 to 4carbon atoms and may be alike or different from each other, and a cationof any other metal, which is able to form water-soluble salts withbenzosulfonic acids; m₁, m₂ and m₃ each represent a whole number from 0to 5 which may be the same or different from each other and n₁, n₂ andn₃ each represent a whole number from 0 to 3, which may be the same ordifferent from each other, whereby at least one of these numbers n₁, n₂and n₃ equals at least one and further comprising a compound selectedfrom the group consisting of a transition metal or a transitionmetal-containing compound.
 2. The process as defined in claim 1, whereinthe diene is a diene having 4 to about 20 carbon atoms.
 3. The processas defined in claim 1, wherein the ratio between the amount of diene andof telomerizing compound is equivalent to at least one molecule of dieneper ten atom of mobile hydrogen.
 4. The process as defined in claim 1,wherein Ar₁, Ar₂ and Ar₃ each represent phenyl.
 5. The process asdefined in claim 1, wherein Y₁, Y₂ and Y₃, which may be alike ordifferent from each other, each represent an alkyl group containing 1 to2 carbon atoms, an alkoxy group containing 1 to 2 carbon atoms orchlorine.
 6. The process as defined in claim 1, wherein M represents aproton, a cation derived from sodium, potassium, calcium or barium,ammonium, tetramethyl ammonium, tetraethyl ammonium, tetrapropylammonium or tetrabutyl ammonium.
 7. The process as defined in claim 1,wherein m₁, m₂ and m₃, which may be alike or different from each othereach represent a whole number between 0 and
 3. 8. The process as definedin claim 1, wherein Ar₁, Ar₂ and Ar₃ each represent phenyl, Y₁, Y₂ andY₃, which may be alike or different from each other, each represent analkyl group containing 1 to 2 carbon atoms, an alkoxy group containing 1to 2 carbon atoms or chlorine, M represents a cation of the groupconsisting of a proton, a cation derived from sodium, potassium, calciumor barium, ammonium, tetramethyl ammonium, tetraethyl ammonium,tetrapropyl ammonium or tetrabutyl ammonium and m₁, m₂ and m₃, which maybe alike or different from each other each represent a whole numberbetween 0 and
 3. 9. The process as defined in claim 1, wherein Ar₁, Ar₂and Ar₃ each represent phenyl, n₁ represents 1, n₂, n₃ m₁, m₂ and m₃each represent zero, and M represents a proton, a cation derived fromsodium, potassium, calcium or barium, ammonium, tetramethyl ammonium ortetraethyl ammonium,
 10. The process as defined in claim 1, wherein Ar₁,Ar₂ and Ar₃ each represent phenyl, n₁ and n₂ each represent 1, m₁, m₂,m₃ and n₃ each represent zero, and M represents a proton, a cationderived from sodium, potassium, calcium or barium, ammonium, tetramethylammonium or tetraethyl ammonium.
 11. The process as defined in claim 1,wherein Ar₁, Ar₂ and Ar₃ each represent phenyl, n₁, n₂ and n₃ eachrepresent 1, m₁, m₂ and m₃ each represent zero, and M represents aproton, a cation derived from sodium, potassium, calcium or barium,ammonium, tetramethyl ammonium or tetraethyl ammonium.
 12. The processas defined in claim 7, wherein at least one of the sulfo groups whichare present therein in each of the phenyl groups Ar₁, Ar₂ or Ar₃ issituated in m-position.
 13. The process as defined in claim 1, whereinthe transition metal is a metal from the group of palladium, nickel,platinum, cobalt, and rhodium.
 14. The process as defined in claim 13,wherein the transition compound is palladium.
 15. The process as definedin claim 14, wherein the palladium is deposited onto an inert carriermaterial.
 16. The process as defined in claim 13, wherein at least partof the transition metal is zero valent.
 17. The process as defined inclaim 1, wherein the transition metal-containing compound is a compoundcontaining palladium, nickel, platinum, cobalt or rhodium.
 18. Theprocess as defined in claim 17, wherein the transition metal-containingcompound is a palladium compound.
 19. The process as defined in claim18, wherein the palladium compound is a compound from the group ofpalladium-acetate, -carboxylate, -carbonate, -borate, -bromide,-chloride, -iodide, -citrate, -hydroxide, -nitrate, -sulfate,-arylsulfonates, -alkylsulfonates, -acetylacetonate,bis(benzonitrile)palladium chloride, and potassium tetrachloropalladate.
 20. The process as defined in claim 18, wherein the palladiumcompound is a compound from the group of bis(cyclooctadiene-1,5)(palladium (zero), tetra (triphenylphosphine) palladium (zero), andpotassium tetracyano palladate.
 21. The process as defined in claim 1,wherein the reaction is effected in the presence of a reducing agentcapable of reducing the transition metal.
 22. The process as defined inclaim 21, wherein the reducing agent is an agent from the group ofsodium borohydride [BH₄ Na], potassium borohydride, zinc powder, andmagnesium.
 23. The process as defined in claim 1, wherein the amount oftransition metal is from about 10⁻⁴ to about 1 gram atom per liter. 24.The process as defined in claim 23, wherein the amount of transitionmetal is from about 0.005 to about 0.5 gram atom per liter.
 25. Theprocess as defined in claim 1, wherein the amount of a phosphine of theformula (I) is from about 0.5 to 2,000 moles per gram atom of transitionmetal.
 26. The process as defined in claim 25, wherein the amount of aphosphine of formula (I) is from about 1 to about 30 moles per gram atomof transition metal.
 27. The process as defined in claim 1, wherein thereaction is effected in the presence of an additive selected from thegroup consisting of a basic compound and a mixture of a basic compoundand an acid.
 28. The process as defined in claim 27, wherein theadditive is selected from the group consisting of alkaline metalhydroxide, alkaline earth metal hydroxides, tertiary aliphatic amines,tertiary aromatic amines and phenolates.
 29. The process as defined inclaim 27, wherein the acid is a mineral acid of an element of the GroupsIIIA, IVA, VA, VIA and VIIA of the periodic system.
 30. The process asdefined in claim 27, wherein the acid is a carbocyclic arylsulfonic oralkylsulfonic acid.
 31. The process as defined in claim 27, wherein thetelomerizing agent is water and the additive is selected from the groupconsisting of alkaline carbonates, alkaline bicarbonates, sodiumsilicates and alkaline salts of phosphorus acid, phosphoric acid andarsenic acid.
 32. The process as defined in claim 31, wherein theadditive is sodium carbonate.
 33. The process as defined in claim 1,wherein the reaction mixture comprises an organic water immisciblesolvent.
 34. The process as defined in claim 33, wherein the solvent isa solvent of the group of benzene, benzonitrile, acetophenone, ethylether, propyl ether, isopropyl ether, methylethylketone andpropionitrile.
 35. The process as defined in claim 1, wherein thereaction mixture further comprises on organic water miscible solvent.36. The process as defined in claim 35, wherein the solvent is a solventof the group of acetone, acetonitrile, dimethylether of diethyleneglycol and dimethoxyethane, dioxane, tert. butanol, dimethyl acetamide,n-methyl pyrolidone and ethylene carbonate.
 37. The process as definedin claim 1, wherein the reaction is performed at a temperature betweenabout -20° C. and about 200° C.
 38. The process as defined in claim 1,which comprises reacting butadiene with water whereby octadiene-2,7-ol-1is formed.
 39. The process as defined in claim 2, wherein the diene is adiene having 4 to about 8 carbon atoms.
 40. The process as defined inclaim 3, wherein the diene is selected from the group consisting ofbutadiene, isoprene, piperylene and dimethylbutadiene.
 41. The processas defined in claim 1, the said catalytic system being present inaqueous solution.